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CN106631953A - Preparation method of beta-carotene in paprika - Google Patents

Preparation method of beta-carotene in paprika Download PDF

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CN106631953A
CN106631953A CN201611247413.5A CN201611247413A CN106631953A CN 106631953 A CN106631953 A CN 106631953A CN 201611247413 A CN201611247413 A CN 201611247413A CN 106631953 A CN106631953 A CN 106631953A
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pigment
carotene
leachate
fructus capsici
solvent
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CN106631953B (en
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金子恒
刘益红
潘天义
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HENAN ZHONGDA BIOLOGICAL ENGINEERING Co Ltd
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HENAN ZHONGDA BIOLOGICAL ENGINEERING Co Ltd
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

本发明属于食品技术领域,特别涉及一种辣椒中β‑胡萝卜素的制备方法。该提取方法包括:将辣椒干燥、粉碎、造粒和浸提,得到色素浸出液;色素浸出液经脱辣后,采用湿法连续上样进行层析分离,分别得到两种洗脱液。洗脱液经浓缩得到辣椒黄色素和辣椒红色素;辣椒黄色素经皂化、沉淀、过滤、真空干燥,得到β‑胡萝卜素产品。本发明首次采用辣椒作为原料制备天然β‑胡萝卜素,在红黄分离的基础上,不仅弥补了以甜椒为原料的辣椒产品单一化发展的缺陷,而且提高了辣椒红的色素的利用价值,为辣椒产业化发展开辟了新的方向。The invention belongs to the technical field of food, in particular to a preparation method of β-carotene in pepper. The extraction method comprises: drying, pulverizing, granulating and extracting the peppers to obtain a pigment leachate; after despicing the pigment leachate, adopting a wet method to continuously load samples for chromatographic separation to obtain two eluents respectively. The eluate is concentrated to obtain capsanthin and capsanthin; the capsanthin is saponified, precipitated, filtered, and vacuum-dried to obtain β-carotene products. The present invention uses capsicum as a raw material for the first time to prepare natural β-carotene. On the basis of separation of red and yellow, it not only makes up for the defect in the single development of capsicum products that use sweet peppers as raw materials, but also improves the utilization value of the pigment of capsanthin. It has opened up a new direction for the development of pepper industry.

Description

一种辣椒中β-胡萝卜素的制备方法A kind of preparation method of β-carotene in capsicum

技术领域technical field

本发明属于食品添加剂技术领域,具体涉及一种辣椒中β-胡萝卜素的制备方法。The invention belongs to the technical field of food additives, and in particular relates to a preparation method of beta-carotene in pepper.

背景技术Background technique

辣椒红色素(Paprika red pigment)是从成熟红辣椒果皮中提取的天然红色素,主要组分为辣椒红素(Capsanthin)、辣椒玉红素(Capsorubin)、β-胡萝卜素(β-carotene)和玉米黄质(zeaxanthin)等,其显色强度是其他色素的10倍,广泛于食品、饮料、化妆品及医药等行业,是国际上公认的最好的A类红色素。辣椒红色素是红辣椒中呈鲜艳红色的部分。但是由于其多应用于食品等领域,导致其附加值过低,最终影响到整个辣椒红产业以及辣椒产业的长远发展。Paprika red pigment is a natural red pigment extracted from the peel of ripe red pepper, and its main components are capsanthin, capsorubin, β-carotene and Zeaxanthin, etc., whose color intensity is 10 times that of other pigments, is widely used in food, beverage, cosmetics and pharmaceutical industries, and is internationally recognized as the best class A red pigment. Capsanthin is the bright red part of red peppers. However, because it is mostly used in food and other fields, its added value is too low, which will eventually affect the long-term development of the entire red pepper industry and the pepper industry.

传统的辣椒红色素主要制备工艺:将辣椒干燥、粉碎,采用溶剂浸提法得到辣椒红色素的粗提液,然后再采用碱液或乙醇等溶剂萃取脱除辣味物质,并蒸馏出其中的溶剂得到精制的辣椒红色素。The main preparation process of traditional capsanthin: dry and pulverize capsicum, use solvent extraction method to obtain the crude extract of capsanthin, then use lye or ethanol and other solvents to extract and remove spicy substances, and distill out the Solvent to obtain refined capsanthin.

现有辣椒主要开发的方向有辣椒红色素和辣椒油树脂两大类产品,主要应用于饮料、冷饮、烘焙等食品领域及饮料、化妆品等领域。辣椒红本身含有多种活性物质,诸如辣椒红素、辣椒玉红素、β-胡萝卜素等。但是,目前偏红辣椒红的应用领域较广泛,而辣椒黄色素辣椒产品开发深度不够,无法体现其本身所还有的β-胡萝卜素、玉米黄质和叶黄素等物质的价值,从而导致辣椒红色素黄红分离成本过高,却无法收到其对应的经济价值。The main development direction of the existing peppers are capsanthin and capsicum oleoresin, which are mainly used in beverages, cold drinks, baking and other food fields, as well as beverages, cosmetics and other fields. Capsanthin itself contains a variety of active substances, such as capsanthin, capsanthin, β-carotene and so on. However, at present, reddish capsanthin has a wide range of application fields, and the development of capsicum yellow pigment capsicum products is not deep enough to reflect the value of β-carotene, zeaxanthin and lutein, etc. The yellow-red separation cost of capsanthin is too high, but its corresponding economic value cannot be received.

β-胡萝卜素是类胡萝卜素之一,也是橘黄色脂溶性化合物,它是自然界中最普遍存在的天然色素,诸如绿色蔬菜、甘薯、胡萝卜、辣椒、盐藻等都含有较丰富β-胡萝卜素。β-carotene is one of the carotenoids, and it is also an orange-yellow fat-soluble compound. It is the most common natural pigment in nature, such as green vegetables, sweet potatoes, carrots, peppers, salina, etc. are rich in β-carotene .

β-胡萝卜素是类胡萝卜素中的一种,胡萝卜素有α、β、γ三种异构体,其中β-异构体含量占80%以上。β-胡萝卜素(β-carotene)又称为β-叶红素,其结构式如下:β-carotene is one of the carotenoids. Carotene has three isomers of α, β, and γ, and the content of β-isomer accounts for more than 80%. β-carotene, also known as β-carotene, has the following structural formula:

其分子式为C40H56,分子量为536.88。β-胡萝卜素有各种顺反不同异构体,例如全反式-β-胡萝卜素、9-顺式-β-胡萝卜素、15-顺式-β-胡萝卜素等。天然β-胡萝卜素为反式和顺式的混合构型,合成β-胡萝卜素为全反式构型。但从分子结构上看,天然β-胡萝卜素和合成β-胡萝卜素是没有差异的,化学和物理性质也没什么差异。Its molecular formula is C 40 H 56 , and its molecular weight is 536.88. β-carotene has various cis-trans isomers, such as all-trans-β-carotene, 9-cis-β-carotene, 15-cis-β-carotene, etc. Natural β-carotene is a mixed configuration of trans and cis, and synthetic β-carotene is an all-trans configuration. But from the perspective of molecular structure, there is no difference between natural β-carotene and synthetic β-carotene, and there is no difference in chemical and physical properties.

β-胡萝卜素目前广泛应用于食品、饲料添加剂、化妆品助剂上。近年研究表明:β-胡萝卜素具有抗氧化和光保护作用。在膳食中经常摄取丰富胡萝卜素的人群,患动脉硬化、某些癌肿以及退行性眼疾等疾病的机会都明显低于摄取较少胡萝卜素的人群,很多动物实验也证明了这一观点。例如:眼睛的视力取决于眼底的黄斑,如果没有足够的β-胡萝卜素来作保护与支持,这个部位就会发生退行性的病变,也就是老化了,视力会衰退甚至最终发生夜盲。这种疾病多发于老年人,虽然医学界认为这是衰老的一种表现,但却同时指出这种退行性眼疾是可以通过摄取足够的β-胡萝卜素来预防的。这一重大发现让人们对胡萝卜素有了新的认识,认为它不仅是实现均衡营养所必需的物质,同时还有助于人们预防疾病、延年益寿,提升身体素质和生活质量。β-carotene is currently widely used in food, feed additives, and cosmetic additives. Recent studies have shown that: β-carotene has antioxidant and photoprotective effects. People who often take in rich carotene in their diet have significantly lower chances of suffering from diseases such as arteriosclerosis, certain cancers, and degenerative eye diseases than those who take in less carotene. Many animal experiments have also proved this point of view. For example, the vision of the eye depends on the macula in the fundus. If there is not enough β-carotene for protection and support, degenerative lesions will occur in this part, that is, aging, vision will decline and even night blindness will eventually occur. This disease mostly occurs in the elderly. Although the medical profession believes that it is a manifestation of aging, it also points out that this degenerative eye disease can be prevented by taking enough β-carotene. This major discovery gave people a new understanding of carotene, and believed that it is not only a necessary substance for achieving balanced nutrition, but also helps people prevent diseases, prolong life, and improve physical fitness and quality of life.

另外,国内外大量科研资料证实β-胡萝卜素防治癌症有确切疗效。机体内氧自由其泛滥不但会损害正常细胞,且常引起畸变而形成癌症,β-胡萝卜素恰恰是氧自由基最强的“克星”。科研证实,癌症病人血中β胡萝卜素远远低于正常人。癌症患者接受放疗和化疗时,β-胡萝卜素能降低其毒副反应。放疗能诱发产生氧自由基,而细胞微粒体膜完整性能阻止氧自由基产生,β-胡萝卜素能维护微粒体膜完整;化疗药物在杀灭癌细胞同时,可使正常细胞致突变,而β-胡萝卜素有抗突变作用,从而减少其毒副反应。In addition, a large number of scientific research data at home and abroad have confirmed that β-carotene has definite curative effect on cancer prevention and treatment. The flood of free oxygen in the body will not only damage normal cells, but also often cause distortion and form cancer. β-carotene is precisely the strongest "nemesis" of oxygen free radicals. Scientific research has confirmed that the β-carotene in the blood of cancer patients is far lower than that of normal people. When cancer patients receive radiotherapy and chemotherapy, β-carotene can reduce their toxic and side effects. Radiotherapy can induce the production of oxygen free radicals, and the integrity of cell microsomal membranes can prevent the production of oxygen free radicals, and β-carotene can maintain the integrity of microsomal membranes; chemotherapy drugs can cause mutations in normal cells while killing cancer cells, while β-carotene can -Carotene has an anti-mutagenic effect, thereby reducing its toxic and side effects.

目前,β-胡萝卜素的来源主要有合成、微生物发酵和天然植物提取三种方式。但随着人们健康理念的不断提高,追求天然已然成为一种趋势,天然β-胡萝卜素的需求量也越来越大。但是能够为提取β-胡萝卜素提供足够原料的植物资源却不多,成为天然提取的β-胡萝卜素实现工业化的生产瓶颈。At present, there are three main sources of β-carotene: synthesis, microbial fermentation and natural plant extraction. However, with the continuous improvement of people's health concept, the pursuit of natural has become a trend, and the demand for natural β-carotene is also increasing. However, there are not many plant resources that can provide enough raw materials for the extraction of β-carotene, which has become a bottleneck for the industrial production of naturally extracted β-carotene.

发明内容Contents of the invention

为了克服背景技术所述的不足,本发明提供一种辣椒中β-胡萝卜素的制备方法,首次采用辣椒作为原料制备天然β-胡萝卜素,在红黄分离的基础上,不仅弥补了以甜椒为原料的辣椒产品单一化发展的缺陷,而且提高了辣椒红的色素的利用价值,为辣椒产业化发展开辟了新的方向。In order to overcome the deficiencies described in the background technology, the present invention provides a preparation method of β-carotene in capsicum. For the first time, capsicum is used as a raw material to prepare natural β-carotene. It is the defect of the unitary development of the pepper product as raw material, and improves the utilization value of the pigment of capsanthin, and opens up a new direction for the industrialization development of pepper.

本发明解决其技术问题所采用的技术方案是:The technical solution adopted by the present invention to solve its technical problems is:

一种辣椒中β-胡萝卜素的制备方法,包括以下步骤:A preparation method of beta-carotene in capsicum, comprising the following steps:

(1)制备原料:将成熟辣椒在30-50℃烘干,粉碎,造粒,得到辣椒颗粒;(1) Preparation of raw materials: drying mature peppers at 30-50° C., pulverizing and granulating to obtain pepper granules;

(2)浸提辣椒红色素:将辣椒颗粒输送进入到连续式浸出器内部,在输送过程中通过喷淋管喷淋萃取溶剂,使萃取剂与辣椒颗粒混合均匀,通过萃取溶剂将辣椒红色素浸提出来,得到色素浸出液;(2) Extraction of capsanthin: transport the capsicum granules into the continuous extractor, spray the extraction solvent through the spray pipe during the transportation process, so that the extraction agent and the capsicum granules are evenly mixed, and the capsanthin is extracted by the extraction solvent. Leach out to obtain the pigment leachate;

(3)脱辣处理:将色素浸出液与醇类溶剂在液-液连续萃取器中混合,脱去辣味物质,得到脱辣的色素脱辣浸出液;(3) Despicy treatment: mix the pigment extract and alcohol solvent in a liquid-liquid continuous extractor to remove the spicy substances to obtain the despiced pigment and despicy extract;

(4)脱去醇类溶剂残留:将色素脱辣浸出液和饱和食盐水在液-液连续萃取器中混合进行脱去醇类溶剂残留处理;(4) Removal of alcohol solvent residues: mixing the pigment depigmentation extract and saturated saline in a liquid-liquid continuous extractor to remove alcohol solvent residues;

(5)层析分离:a)将步骤(4)得到的色素浸出液直接上硅胶柱进行吸附分离,并收集端口流出液;b)待硅胶柱吸附饱和后,采用烷烃类洗脱剂对硅胶柱进行洗脱,洗脱液与端口流出液合并得辣椒黄色素洗脱液,将辣椒黄色素洗脱液进行浓缩得辣椒黄色素;c)用丙酮对硅胶柱进行洗脱,得丙酮洗脱液,将所述丙酮洗脱液浓缩,得到辣椒红色素;(5) Chromatographic separation: a) the pigment leachate obtained in step (4) is directly applied to a silica gel column for adsorption and separation, and the port effluent is collected; For elution, the eluate is combined with the port effluent to obtain a capsanthin eluate, and the capsanthin eluate is concentrated to obtain capsanthin; c) eluting the silica gel column with acetone to obtain an acetone eluate , concentrating the acetone eluent to obtain capsanthin;

(6)皂化精制:a)将辣椒黄色素与碱性醇类溶液混合,在水浴搅拌条件下进行皂化反应;b)皂化完毕后,采用酸性溶液调节pH至4.0-9.0,采用醇类溶剂在水浴搅拌条件下进行稀释处理,静置析晶,过滤,得到皂化滤液和β-胡萝卜素粗品;c)采用醇类溶剂对β-胡萝卜素粗品经洗涤,过滤得到滤饼和粗品洗涤液,滤饼即为β-胡萝卜素精品,减压干燥β-胡萝卜素精品即得到β-胡萝卜素精品;d)将皂化滤液与粗品洗涤液合并,浓缩至无水乙醇残留,得到膏状副产物;(6) Saponification refining: a) mix capsicum yellow with alkaline alcohol solution, and carry out saponification reaction under water bath stirring condition; b) after saponification, use acidic solution to adjust pH to 4.0-9.0, use alcohol solvent in Dilution treatment is carried out under the condition of stirring in a water bath, standing for crystallization, and filtering to obtain the saponification filtrate and crude β-carotene; c) washing the crude β-carotene with an alcohol solvent, filtering to obtain a filter cake and a crude washing solution, and filtering The cake is the fine β-carotene, and the fine β-carotene is dried under reduced pressure to obtain the fine β-carotene; d) The saponification filtrate is combined with the crude product washing liquid, concentrated to the residue of absolute ethanol, and a paste-like by-product is obtained;

(7)萃取副产物:将膏状副产物用水溶解,并用有机溶剂进行萃取、静置、分层,上层溶液经浓缩回收溶剂,得油膏状色素产品;下层经脱除有机溶剂处理后,采用喷雾干燥得到粉体辣椒黄产品。(7) Extraction of by-products: dissolving the paste-like by-products in water, and extracting with an organic solvent, standing, and layering, the upper layer solution is concentrated and recovered to obtain a paste-like pigment product; the lower layer is processed by removing the organic solvent, The powder capsicum yellow product is obtained by spray drying.

优选的,步骤(2)中,连续式浸出器为平转式浸出器、环形浸出器、卫星式浸出器或履带式浸出器;萃取溶剂为植物油抽提溶剂,植物油抽提溶剂的标准按照GB 16629-2008植物油抽提溶剂来执行;喷淋管喷淋温度为40-50℃,喷淋量为1000-1500L/h。Preferably, in step (2), the continuous extractor is a horizontal extractor, an annular extractor, a satellite extractor or a crawler extractor; the extraction solvent is a vegetable oil extraction solvent, and the standard for the vegetable oil extraction solvent is in accordance with GB 16629-2008 Vegetable Oil Extraction Solvent; the spray temperature of the spray pipe is 40-50°C, and the spray volume is 1000-1500L/h.

优选的,步骤(3)中,醇类溶剂为甲醇、乙醇、丙醇、异丙醇或丁醇中的一种;反应体系的温度为30-50℃;色素浸出液流量为0.5-1.5m3/h,醇类溶剂的流量为1-3m3/h;液-液连续萃取器中上层为色素浸出液,下层为醇类溶剂,醇类溶剂萃取色素浸出液中的辣椒素、二氢辣素和降二氢辣素等辣味物质,脱除辣味物质后,得到脱辣的色素脱辣浸出液。Preferably, in step (3), the alcoholic solvent is one of methanol, ethanol, propanol, isopropanol or butanol; the temperature of the reaction system is 30-50°C; the flow rate of the pigment leachate is 0.5-1.5m3 /h, the flow rate of the alcohol solvent is 1-3m 3 /h; the upper layer in the liquid-liquid continuous extractor is the pigment leachate, the lower layer is the alcohol solvent, and the alcohol solvent extracts capsaicin, dihydrocapsaicin and Pungent substances such as nordihydrocapsaicin are removed to obtain a despiced pigment despiced extract.

优选的,步骤(4)中,色素脱辣浸出液流量为1-3m3/h,饱和食盐水流量为0.5-1.5m3/h,液-液连续萃取器中上层为色素脱辣浸出液,下层为饱和食盐水,饱和食盐水萃取色素脱辣浸出液中残留的醇类溶剂。Preferably, in step (4), the flow rate of the pigment despicing leachate is 1-3m 3 /h, the flow rate of saturated saline is 0.5-1.5m 3 /h, the upper layer in the liquid-liquid continuous extractor is the pigment despicing leachate, the lower layer It is saturated saline, and the saturated saline extracts the residual alcohol solvent in the leachate of pigment despicing.

优选的,步骤(5)中,步骤b)中用的洗脱剂为植物油抽提溶剂,植物油抽提溶剂洗脱速度为0.2-2Bv/h,植物油抽提溶剂与硅胶柱体积比为2-4:1;步骤b)中采用的浓缩方式为减压浓缩,压力为-0.03~-0.06Mpa,浓缩的温度为40-100℃;步骤c)中丙酮与硅胶体积比为2-4:1,丙酮洗脱速度为0.2-2Bv/h。Preferably, in step (5), the eluent used in step b) is a vegetable oil extraction solvent, the vegetable oil extraction solvent elution rate is 0.2-2Bv/h, and the vegetable oil extraction solvent and silica gel column volume ratio is 2- 4:1; the concentration method used in step b) is vacuum concentration, the pressure is -0.03~-0.06Mpa, the concentration temperature is 40-100°C; the volume ratio of acetone to silica gel in step c) is 2-4:1 , Acetone elution rate is 0.2-2Bv/h.

优选的,步骤(6)中,步骤a)中碱性醇类溶液为KOH的醇溶液,水浴温度为40-50℃,搅拌条件为150-200r/min,皂化反应温度为50-60℃,皂化时间为2.5-3h;步骤b)中酸性溶液为盐酸,醇类溶剂为浓度60-70%的乙醇,水浴温度为40-50℃,搅拌条件为150-200r/min,析晶的温度为40℃,过滤时滤布孔径为500目;步骤c)中采用的醇类溶剂为浓度60-70%的乙醇,减压干燥的真空度为-0.08~-0.09MPa,减压干燥温度为45-50℃;步骤d)中采用减压浓缩的方式,浓缩温度为70-75℃,浓缩的真空度为-0.06~-0.08Mpa。Preferably, in step (6), the alkaline alcohol solution in step a) is an alcohol solution of KOH, the water bath temperature is 40-50°C, the stirring condition is 150-200r/min, and the saponification reaction temperature is 50-60°C, The saponification time is 2.5-3h; the acidic solution in step b) is hydrochloric acid, the alcoholic solvent is ethanol with a concentration of 60-70%, the water bath temperature is 40-50°C, the stirring condition is 150-200r/min, and the crystallization temperature is 40 DEG C, filter cloth pore diameter is 500 meshes during filtration; The alcoholic solvent that adopts in the step c) is the ethanol of concentration 60-70%, the vacuum degree of decompression drying is-0.08~-0.09MPa, and decompression drying temperature is 45 -50°C; step d) adopts the method of concentrating under reduced pressure, the concentration temperature is 70-75°C, and the vacuum degree of concentration is -0.06~-0.08Mpa.

优选的,步骤(7)中,副产物与水的比例为1:1,有机溶剂为乙酸乙酯,副产物溶液与有机溶剂为1:1,喷雾干燥进口温度为185-195℃,喷雾干燥出口温度为85-90℃。Preferably, in step (7), the ratio of by-products to water is 1:1, the organic solvent is ethyl acetate, the ratio of by-product solution and organic solvent is 1:1, the spray drying inlet temperature is 185-195°C, and the spray drying The outlet temperature is 85-90°C.

本发明的优点是:首次采用辣椒作为原料制备天然β-胡萝卜素,在红黄分离的基础上,不仅弥补了以甜椒为原料的辣椒产品单一化发展的缺陷,而且提高了辣椒红的色素的利用价值,为辣椒产业化发展开辟了新的方向。The advantages of the present invention are: for the first time, capsicum is used as raw material to prepare natural β-carotene. On the basis of separation of red and yellow, it not only makes up for the defect of single development of capsicum products with sweet pepper as raw material, but also improves the pigment of capsanthin The utilization value has opened up a new direction for the development of pepper industry.

具体实施方式detailed description

下面将结合实施例对本发明作进一步的说明:The present invention will be further described below in conjunction with embodiment:

实施例1Example 1

a)取成熟辣椒10t,干燥,粉碎后造粒,采用平转式连续浸出器萃取得到色素浸出液。将所述色素浸出液与70%乙醇在液-液萃取器中于45℃,200r/min条件下混合脱除辣味物质,色素浸出液流量为1m3/h,70%乙醇流量为2m3/h,得到脱辣的色素辣浸出液。将所述脱辣的色素辣浸出液与饱和食盐水于200r/min条件下混合脱除色素萃取液中残留的乙醇,脱辣得色素萃取液流量为1.8m3/h,饱和食盐水的流量为0.6m3/h,得到脱辣的色素浸出液。a) Take 10t of mature peppers, dry them, crush them and granulate them, and extract them with a flat-rotating continuous extractor to obtain a pigment extract. Mix the pigment leachate with 70% ethanol in a liquid-liquid extractor at 45°C and 200r/min to remove the spicy substance, the flow rate of the pigment leachate is 1m 3 /h, and the flow rate of 70% ethanol is 2m 3 /h , to get off the peppery pigment spicy leachate. Mix the depigmented spicy extract with saturated saline at 200r /min to remove residual ethanol in the depigmented extract. 0.6m 3 /h to obtain a despiced pigment extract.

b)将所述脱除残留乙醇的色素浸出液采用连续湿法上样的方式以1Bv/h流速进行硅胶柱层析分离,收集下端口流出液。先用5000L植物油抽提溶剂以0.3Bv/h流速进行洗脱,洗脱液与下端口收集液合并,得到辣椒黄色素洗脱液。将所述辣椒黄色素洗脱液采用减压浓缩得到深黄色辣椒黄色素201.6Kg,色价173.5,A470/A454为0.848。然后采用7000L丙酮以0.3Bv/h流速对硅胶柱进行洗脱,得到丙酮洗脱液。将所述丙酮洗脱液采用减压浓缩得到深红色辣椒红色素298.7Kg,色价为338.7,A470/A454为1.024。b) The pigment leachate from which residual ethanol has been removed is subjected to silica gel column chromatography at a flow rate of 1 Bv/h by continuous wet loading, and the effluent from the lower port is collected. First use 5000L vegetable oil extraction solvent to elute at a flow rate of 0.3Bv/h, and combine the eluate with the liquid collected from the lower port to obtain the capsanthin eluate. The capsanthin eluate was concentrated under reduced pressure to obtain 201.6 Kg of dark yellow capsanthin with a color value of 173.5 and A 470 /A 454 of 0.848. Then, 7000 L of acetone was used to elute the silica gel column at a flow rate of 0.3 Bv/h to obtain an acetone eluate. The acetone eluate was concentrated under reduced pressure to obtain 298.7 Kg of deep red capsanthin with a color value of 338.7 and A 470 /A 454 of 1.024.

c)取辣椒黄色素200Kg置皂化反应罐中,在150r/min搅拌条件下加入240Kg氢氧化钾-70%乙醇(氢氧化钾浓度为20%),于60℃水浴皂化反应3h。反应完毕,采用10%的盐酸调节pH至7.5,然后向反应液中加入480Kg70%的乙醇,于40℃,150r/min条件搅拌30min。停止搅拌后,趁热过400目滤布,收集滤饼,得到β-胡萝卜素粗品。向滤饼中加入200Kg的70%乙醇,于40℃,150r/min条件搅拌30min。停止搅拌后,趁热过400目滤布,收集滤饼。将滤饼于55℃,-0.09Mpa条件下真空干燥15h,得到15.1Kgβ-胡萝卜素精品,色价为1084.6,A470/A454为0.868。合并两次滤液,于70℃,-0.08Mpa条件下减压浓缩回收至无乙醇,加入150Kg乙酸乙酯,于室温,150r/min条件下搅拌20min。停止搅拌后,静置分层1h。取下层液于60℃,-0.06Mpa条件下回收残留乙酸乙酯,得色素水溶液,加入10Kg的麦芽糊精混匀后,于进口温度190℃,出口温度90℃条件下进行喷雾干燥,得到粉体辣椒黄产品148Kg,色价为23.8。上层乙酸乙酯溶液于50℃,-0.06Mpa条件下浓缩回收溶剂,得到油膏状辣椒黄色素89.7Kg,色价为150.9,A470/A454为0.862。c) Take 200Kg of capsicum yellow pigment and place it in a saponification reaction tank, add 240Kg of potassium hydroxide-70% ethanol (concentration of potassium hydroxide is 20%) under the stirring condition of 150r/min, and saponify in a 60°C water bath for 3h. After the reaction is completed, adjust the pH to 7.5 with 10% hydrochloric acid, then add 480Kg of 70% ethanol to the reaction solution, and stir at 40°C and 150r/min for 30min. After stopping the stirring, pass through a 400-mesh filter cloth while it is hot, collect the filter cake, and obtain the crude product of β-carotene. Add 200Kg of 70% ethanol to the filter cake, and stir for 30min at 40°C and 150r/min. After stopping stirring, pass through a 400-mesh filter cloth while hot to collect the filter cake. The filter cake was vacuum-dried at 55°C and -0.09Mpa for 15 hours to obtain 15.1Kg of refined β-carotene with a color value of 1084.6 and A 470 /A 454 of 0.868. Combine the two filtrates, concentrate under reduced pressure at 70°C and -0.08Mpa to recover ethanol-free, add 150Kg ethyl acetate, and stir at room temperature and 150r/min for 20min. After stopping stirring, let the layers stand for 1h. Take the lower layer and recover the residual ethyl acetate under the conditions of 60°C and -0.06Mpa to obtain a pigment aqueous solution, add 10Kg of maltodextrin and mix well, then spray dry at an inlet temperature of 190°C and an outlet temperature of 90°C to obtain a powder The body pepper yellow product is 148Kg, and the color value is 23.8. The ethyl acetate solution in the upper layer was concentrated at 50°C and -0.06Mpa to recover the solvent to obtain 89.7Kg of oily capsanthin with a color value of 150.9 and A 470 /A 454 of 0.862.

实施例2Example 2

a)取成熟辣椒10t,干燥,粉碎后造粒,采用平转式连续浸出器萃取得到色素浸出液。将所述色素浸出液与70%乙醇在液-液萃取器中于50℃,200r/min条件下混合脱除辣味物质,色素浸出液流量为1m3/h,70%乙醇流量为1.5m3/h,得到脱辣的色素辣浸出液。将所述脱辣的色素辣浸出液与饱和食盐水于200r/min条件下混合脱除色素萃取液中残留的乙醇,脱辣得色素浸出液流量为1.5m3/h,饱和食盐水的流量为0.5m3/h,得到脱辣的色素浸出液。a) Take 10t of mature peppers, dry them, crush them and granulate them, and extract them with a flat-rotating continuous extractor to obtain a pigment extract. Mix the pigment extract and 70% ethanol in a liquid - liquid extractor at 50°C and 200r /min to remove the spicy substances. h, to obtain the hot-pigmented spicy leachate. Mix the despiced pigmented leachate with saturated saline at 200r/min to remove the residual ethanol in the depigmented extract. m 3 /h to obtain a despiced pigment extract.

b)将所述脱除残留乙醇的色素浸出液采用连续湿法上样的方式以0.8Bv/h流速进行硅胶柱层析分离,收集下端口流出液。先用6500L植物油抽提溶剂以0.5Bv/h流速进行洗脱,洗脱液与下端口收集液合并,得到辣椒黄色素洗脱液。将所述辣椒黄色素洗脱液采用减压浓缩得到深黄色辣椒黄色素178Kg,色价为186.8,A470/A454为0.862。然后采用7800L丙酮以0.5Bv/h流速对硅胶柱进行洗脱,得到丙酮洗脱液。将所述丙酮洗脱液采用减压浓缩得到深红色辣椒红色素279.8Kg,色价为344.6,A470/A454为1.023。b) The pigment leachate from which residual ethanol has been removed is subjected to silica gel column chromatography at a flow rate of 0.8 Bv/h by continuous wet loading, and the effluent from the lower port is collected. First use 6500L vegetable oil extraction solvent to elute at a flow rate of 0.5Bv/h, and combine the eluate with the liquid collected from the lower port to obtain the capsanthin eluate. The capsanthin eluate was concentrated under reduced pressure to obtain 178Kg of dark yellow capsanthin with a color value of 186.8 and A 470 /A 454 of 0.862. Then, 7800 L of acetone was used to elute the silica gel column at a flow rate of 0.5 Bv/h to obtain an acetone eluate. The acetone eluate was concentrated under reduced pressure to obtain 279.8 Kg of deep red capsanthin with a color value of 344.6 and A 470 /A 454 of 1.023.

c)取辣椒黄色素175Kg置皂化反应罐中,在150r/min搅拌条件下加入140Kg氢氧化钾-80%乙醇(氢氧化钾浓度为30%),于60℃水浴皂化反应3h。反应完毕,采用10%的盐酸调节pH至6.2,然后向反应液中加入300Kg80%的乙醇,于40℃,150r/min条件搅拌30min。停止搅拌后,趁热过500目滤布,收集滤饼,得到β-胡萝卜素粗品。向滤饼中加入150Kg的80%乙醇,于40℃,150r/min条件搅拌30min。停止搅拌后,趁热过500目滤布,收集滤饼。将滤饼于50℃,-0.09Mpa条件下真空干燥12h,得到13.8Kgβ-胡萝卜素精品,色价为1206.4,A470/A454为0.872。合并两次滤液,于70℃,-0.08Mpa条件下减压浓缩回收至无乙醇,加入100Kg乙酸乙酯,于室温,150r/min条件下搅拌30min。停止搅拌后,静置分层1h。取下层液于50℃,-0.06Mpa条件下回收残留乙酸乙酯,得色素水溶液,加入10Kg麦芽糊精混匀,于进口温度180℃,出口温度80℃条件下进行喷雾干燥,得到粉体辣椒黄产品136.8Kg,色价为25.6。上层乙酸乙酯溶液于50℃,-0.06Mpa条件下浓缩回收溶剂,得到油膏状辣椒黄色素73.8Kg,色价为153.7,A470/A454为0.844。c) Take 175Kg of capsicum yellow pigment and place it in a saponification reaction tank, add 140Kg of potassium hydroxide-80% ethanol (concentration of potassium hydroxide is 30%) under stirring condition of 150r/min, and saponify in a 60°C water bath for 3h. After the reaction is completed, adjust the pH to 6.2 with 10% hydrochloric acid, then add 300Kg of 80% ethanol to the reaction solution, and stir at 40°C and 150r/min for 30min. After stopping the stirring, pass through a 500-mesh filter cloth while it is hot, collect the filter cake, and obtain the crude product of β-carotene. Add 150Kg of 80% ethanol to the filter cake, and stir for 30min at 40°C and 150r/min. After stopping stirring, pass through a 500-mesh filter cloth while hot to collect the filter cake. The filter cake was vacuum-dried at 50°C and -0.09Mpa for 12 hours to obtain 13.8Kg of refined β-carotene with a color value of 1206.4 and A 470 /A 454 of 0.872. Combine the two filtrates, concentrate under reduced pressure at 70°C and -0.08Mpa to recover ethanol-free, add 100Kg ethyl acetate, and stir at room temperature and 150r/min for 30min. After stopping stirring, let the layers stand for 1h. Take the lower layer liquid and recover residual ethyl acetate under the condition of 50°C and -0.06Mpa to obtain a pigment aqueous solution, add 10Kg of maltodextrin and mix well, and spray dry at an inlet temperature of 180°C and an outlet temperature of 80°C to obtain powdered pepper The yellow product weighs 136.8Kg and has a color value of 25.6. The ethyl acetate solution in the upper layer was concentrated at 50°C and -0.06Mpa to recover the solvent to obtain 73.8Kg of capsanthin in the form of ointment, with a color value of 153.7 and A 470 /A 454 of 0.844.

实施例3Example 3

a)取成熟辣椒10t,干燥,粉碎后造粒,采用平转式连续浸出器萃取得到色素浸出液。将所述色素浸出液与70%乙醇在液-液萃取器中于50℃,200r/min条件下混合脱除辣味物质,色素浸出液流量为1m3/h,70%乙醇流量为1.5m3/h,得到脱辣的色素辣浸出液。将所述脱辣的色素辣浸出液与饱和食盐水于200r/min条件下混合脱除色素萃取液中残留的乙醇,脱辣得色素浸出液流量为1.5m3/h,饱和食盐水的流量为0.5m3/h,得到脱辣的色素浸出液。a) Take 10t of mature peppers, dry them, crush them and granulate them, and extract them with a flat-rotating continuous extractor to obtain a pigment extract. Mix the pigment extract and 70% ethanol in a liquid - liquid extractor at 50°C and 200r /min to remove the spicy substances. h, to obtain the hot-pigmented spicy leachate. Mix the despiced pigmented leachate with saturated saline at 200r/min to remove the residual ethanol in the depigmented extract. m 3 /h to obtain a despiced pigment extract.

b)将所述脱除残留乙醇的色素浸出液采用连续湿法上样的方式以0.8Bv/h流速进行硅胶柱层析分离,收集下端口流出液。先用5000L植物油抽提溶剂以0.5Bv/h流速进行洗脱,洗脱液与下端口收集液合并,得到辣椒黄色素洗脱液。将所述辣椒黄色素洗脱液采用减压浓缩得到深黄色辣椒黄色素214.3Kg,色价为169.2,A470/A454为0.865。然后采用7200L丙酮以0.5Bv/h流速对硅胶柱进行洗脱,得到丙酮洗脱液。将所述丙酮洗脱液采用减压浓缩得到深红色辣椒红色素304.2Kg,色价为327.3,A470/A454为1.027。b) The pigment leachate from which residual ethanol has been removed is subjected to silica gel column chromatography at a flow rate of 0.8 Bv/h by continuous wet loading, and the effluent from the lower port is collected. First use 5000L vegetable oil extraction solvent to elute at a flow rate of 0.5Bv/h, and combine the eluate with the liquid collected from the lower port to obtain the capsanthin eluate. The capsanthin eluate was concentrated under reduced pressure to obtain 214.3 Kg of dark yellow capsanthin with a color value of 169.2 and A 470 /A 454 of 0.865. Then, 7200 L of acetone was used to elute the silica gel column at a flow rate of 0.5 Bv/h to obtain an acetone eluent. The acetone eluate was concentrated under reduced pressure to obtain 304.2 Kg of deep red capsanthin with a color value of 327.3 and A 470 /A 454 of 1.027.

c)取辣椒黄色素210Kg置皂化反应罐中,在150r/min搅拌条件下加入130Kg氢氧化钾-70%乙醇(氢氧化钾浓度为40%),于50℃水浴皂化反应3h。反应完毕,采用10%的盐酸调节pH至5.0,然后向反应液中加入400Kg70%的乙醇,于50℃,150r/min条件搅拌20min。停止搅拌后,趁热过500目滤布,收集滤饼,得到β-胡萝卜素粗品。向滤饼中加入200Kg的70%乙醇,于50℃,150r/min条件搅拌30min。停止搅拌后,趁热过400目滤布,收集滤饼。将滤饼于60℃,-0.09Mpa条件下真空干燥12h,得到13.8Kgβ-胡萝卜素精品,色价为1394.1,A470/A454为0.865。合并两次滤液,于70℃,-0.08Mpa条件下减压浓缩回收至无乙醇,加入120Kg乙酸乙酯,于室温,150r/min条件下搅拌40min。停止搅拌后,静置分层1.5h。取下层液于70℃,-0.07Mpa条件下回收残留乙酸乙酯,得色素水溶液,加入8Kg麦芽糊精,于进口温度190℃,出口温度90℃条件下进行喷雾干燥,得到粉体辣椒黄产品157.4Kg,色价为20.3。上层乙酸乙酯溶液于60℃,-0.04Mpa条件下浓缩回收溶剂,得到油膏状辣椒黄色素73.2Kg,色价为155.2,A470/A454为0.868。c) Take 210Kg of capsicum yellow pigment and place it in a saponification reaction tank, add 130Kg of potassium hydroxide-70% ethanol (concentration of potassium hydroxide is 40%) under stirring condition of 150r/min, and saponify in a 50°C water bath for 3h. After the reaction is completed, adjust the pH to 5.0 with 10% hydrochloric acid, then add 400Kg of 70% ethanol to the reaction solution, and stir at 50°C and 150r/min for 20min. After stopping the stirring, pass through a 500-mesh filter cloth while it is hot, collect the filter cake, and obtain the crude product of β-carotene. Add 200Kg of 70% ethanol to the filter cake, and stir for 30min at 50°C and 150r/min. After stopping stirring, pass through a 400-mesh filter cloth while hot to collect the filter cake. The filter cake was vacuum-dried at 60°C and -0.09Mpa for 12 hours to obtain 13.8Kg of fine β-carotene with a color value of 1394.1 and A 470 /A 454 of 0.865. Combine the two filtrates, concentrate under reduced pressure at 70°C and -0.08Mpa to recover ethanol-free, add 120Kg ethyl acetate, and stir at room temperature and 150r/min for 40min. After stopping stirring, let the layers stand for 1.5h. Take the lower layer and recover the residual ethyl acetate under the condition of 70°C and -0.07Mpa to obtain a pigment aqueous solution, add 8Kg of maltodextrin, and spray dry at an inlet temperature of 190°C and an outlet temperature of 90°C to obtain a powdered capsicum yellow product 157.4Kg, color value is 20.3. The ethyl acetate solution in the upper layer was concentrated at 60°C and -0.04Mpa to recover the solvent to obtain 73.2Kg of capsanthin in ointment form, with a color value of 155.2 and A 470 /A 454 of 0.868.

对上述实施例制备的β-胡萝卜素产品中的β-胡萝卜素含量进行检测。检测结果如表1所示。The content of β-carotene in the β-carotene products prepared in the above examples was detected. The test results are shown in Table 1.

表1实施例β-胡萝卜素产品组分检测结果Table 1 embodiment β-carotene product component detection result

实施例1Example 1 实施例2Example 2 实施例3Example 3 色价color price 1084.61084.6 1206.41206.4 1394.11394.1 吸光比Absorbance ratio 0.8680.868 0.8720.872 0.8650.865 β-胡萝卜素/%β-carotene/% 32.432.4 38.538.5 41.941.9

最后应说明的是:显然,上述实施例仅仅是为清楚地说明本发明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明的保护范围之中。Finally, it should be noted that obviously, the above-mentioned embodiments are only examples for clearly illustrating the present invention, rather than limiting the implementation. For those of ordinary skill in the art, on the basis of the above description, other changes or changes in different forms can also be made. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims (7)

1. in a kind of Fructus Capsici beta-carotene preparation method, it is characterised in that described preparation method is comprised the following steps:
(1) preparing raw material:By ripe Fructus Capsici in 30-50 DEG C of drying, crush, pelletize obtains Fructus Capsici granule;
(2) capsicum red pigment is extracted:Fructus Capsici granule is delivered into inside continuous way infuser, by spray in course of conveying Shower pipe spraying and extracting solvent, makes extractant mix homogeneously with Fructus Capsici granule, is leached out capsicum red pigment by extractant, Obtain pigment leachate;
(3) peppery process is taken off:Pigment leachate is mixed with alcohols solvent in liquid-liquid continuous extraction device, spicy substance is sloughed, is obtained Peppery leachate is taken off to de- peppery pigment;
(4) alcohols solvent residual is sloughed:Pigment is taken off into peppery leachate and saturated aqueous common salt to be mixed in liquid-liquid continuous extraction device Row sloughs alcohols solvent residual treatment;
(5) chromatography:A) the pigment leachate that step (4) is obtained directly is gone up into silicagel column carries out adsorbing separation, and collecting terminal Mouth effluent;B) after silicagel column adsorption saturation, eluting, eluent and port flow are carried out to silicagel column using alkanes eluant Go out liquid and merge to obtain Fructus Capsici flavochrome eluent, Fructus Capsici flavochrome eluent is carried out being concentrated to give Fructus Capsici flavochrome;C) with acetone pair Silicagel column carries out eluting, obtains acetone eluant, by acetone eluant concentration, obtains capsicum red pigment;
(6) saponification is refined:A) Fructus Capsici flavochrome is mixed with alkaline alcohol solution, saponification is carried out under the conditions of stirring in water bath anti- Should;B) after saponification is finished, pH to 4.0-9.0 is adjusted using acid solution, is carried out under the conditions of stirring in water bath using alcohols solvent Dilution is processed, and stands crystallize, is filtered, and obtains saponification filtrate and beta-carotene crude product;C) using alcohols solvent to beta-carotene Crude product is scrubbed, is filtrated to get filter cake and crude product cleaning mixture, and filter cake is beta-carotene fine work, drying under reduced pressure beta-carotene essence Product obtain beta-carotene fine work;D) saponification filtrate is merged with crude product cleaning mixture, is concentrated into dehydrated alcohol residual, obtain cream Shape by-product;
(7) by-product is extracted:By paste by-product water dissolution, and extracted with organic solvent, stood, be layered, upper strata is molten The concentrated recycling design of liquid, obtains ointment shape pigment product;Lower floor obtains powder Jing after removing organic solvent is processed using spray drying Body Fructus Capsici Huang product.
2. in a kind of Fructus Capsici as claimed in claim 1 beta-carotene preparation method, it is characterised in that in step (2), even Continuous formula infuser is flat rotary extractor, loop type extractor, satellite type infusion device or crawler type infuser;Extractant is plant Oil extraction solvent;Shower spray temperature is 40-50 DEG C, and spray flux is 1000-1500L/h.
3. in a kind of Fructus Capsici as claimed in claim 2 beta-carotene preparation method, it is characterised in that in step (3), alcohol Class solvent is the one kind in methanol, ethanol, propanol, isopropanol or butanol;The temperature of reaction system is 30-50 DEG C;Pigment is leached Flow quantity is 0.5-1.5m3/ h, the flow of alcohols solvent is 1-3m3/h;Liquid-liquid continuous extraction device is at the middle and upper levels pigment leachate, Lower floor is alcohols solvent, the pungent thing such as capsaicin, dihydro Capsaicin and drop dihydro Capsaicin in alcohols solvent extraction pigment leachate Matter, after removing spicy substance, obtains de- peppery pigment and takes off peppery leachate.
4. in a kind of Fructus Capsici as claimed in claim 3 beta-carotene preparation method, it is characterised in that in step (4), color The de- peppery leaching flow quantity of element is 1-3m3/ h, saturated common salt discharge is 0.5-1.5m3/ h, liquid-liquid continuous extraction device is at the middle and upper levels Pigment takes off peppery leachate, and lower floor is saturated aqueous common salt, and saturated aqueous common salt extraction pigment takes off the alcohols solvent remained in peppery leachate.
5. in a kind of Fructus Capsici as claimed in claim 4 beta-carotene preparation method, it is characterised in that in step (5), step It is rapid b) in eluant be vegetable oil extraction solvent, vegetable oil extraction solvent elution speed is 0.2-2Bv/h, plant oil extraction Solvent is 2-4 with silicagel column volume ratio:1;The condensing mode adopted in step b) for concentrating under reduced pressure, pressure for -0.03~- 0.06Mpa, the temperature of concentration is 40-100 DEG C;Acetone and silica gel volume ratio are 2-4 in step c):1, acetone elution speed is 0.2-2Bv/h。
6. in a kind of Fructus Capsici as claimed in claim 5 beta-carotene preparation method, it is characterised in that in step (6), step Rapid a) neutral and alkali alcohol solution for KOH alcoholic solution, bath temperature is 40-50 DEG C, and stirring condition is 150-200r/min, saponification Reaction temperature is 50-60 DEG C, and saponification time is 2.5-3h;Acid solution is hydrochloric acid in step b), and alcohols solvent is concentration 60- 70% ethanol, bath temperature is 40-50 DEG C, and stirring condition is 150-200r/min, and the temperature of crystallize is 40 DEG C, is filtered during filtration Cloth aperture is 500 mesh;The alcohols solvent adopted in step c) for concentration 60-70% ethanol, the vacuum of drying under reduced pressure is- 0.08~-0.09MPa, drying under reduced pressure temperature is 45-50 DEG C;In step d) by the way of concentrating under reduced pressure, thickening temperature is 70- 75 DEG C, the vacuum of concentration is -0.06~-0.08Mpa.
7. in a kind of Fructus Capsici as claimed in claim 6 beta-carotene preparation method, it is characterised in that it is secondary in step (7) The ratio of product and water is 1:1, organic solvent is ethyl acetate, and by-product solution is 1 with organic solvent:1, it is spray-dried import Temperature is 185-195 DEG C, and spray drying exit temperature is 85-90 DEG C.
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